KR101012173B1 - Polyvinyl halide-uncrosslinked elastomer alloy - Google Patents

Abstract

A thermoplastic alloy is disclosed comprising poly(vinyl halide) and an olefin-based uncrosslinked elastomer having thermoplastic properties. The alloy can be made into a polymeric skin using slush molding techniques.

Description

Polyvinyl halide-uncrosslinked elastomer alloy {POLYVINYL HALIDE-UNCROSSLINKED ELASTOMER ALLOY}

The present invention relates to polyvinyl halides, in particular polyvinyl chloride (PVC) and thermoplastic alloys of elastomers which exhibit thermoplasticity because they are not crosslinked.

U.S. Patent Application Publication No. 20040054085 (Tansey) describes a problem in the art of making instrument panel coverstock designed to tear at certain locations to allow release of the airbag from the compartment of the airbag. Low temperatures embrittle the PVC or PVC alloy used as such coverstock for instrument panels so that fragments of coverstock can cause injury to passengers during deployment of the airbag.

Tansey attempted to solve the brittleness problem by dispersing the melt-processable partially crosslinked rubber into the PVC matrix. However, dispersion of partially crosslinked rubber into the polymer does not help the alloy's overall thermoplastic properties. In fact, the crosslinked elastomer, ie rubber, can inhibit the melt processability of the alloy during the formation of the final form of the thermoplastic product. In addition, rubber can reduce the cold temperature performance of the alloy and increase the melt viscosity of the polymer.

Summary of the Invention

The present invention solves the brittleness problem without causing problems associated with the use of crosslinked elastomers, in particular crosslinked elastomers characterized as melt processible rubbers.

One aspect of the invention relates to slush molded articles made from thermoplastic alloys comprising poly (vinyl halides), plasticizers, and olefin-based uncrosslinked elastomers with thermoplastics.

One advantage of the present invention is that the thermoplastic alloy can be processed to form a polymer skin by using slush molding techniques.

Poly (vinyl Halide )

Polyvinyl halides are polymers containing a vinyl moiety and one or more halides bonded thereto. Commercially acceptable polyvinyl halides are poly (vinyl chloride) (“PVC”) and chlorinated poly (vinyl chloride) (“CPVC”) due to availability and cost.

PVC or CPVC is basically a homopolymer of vinyl chloride and, if present, contains small amounts of other co-monomers. CPVC is chlorinated PVC, where PVC containing about 57% of chlorine is further reacted with CPVC, i.e. Produces polymers with higher Tg and heat deflection temperatures. Commercial CPVC typically contains from about 58% to about 70% by weight, preferably from about 63% to about 68% by weight chlorine.

Poly (vinyl chloride) comprises polymerized vinyl chloride monomers wherein the preferred polymers are basically homopolymerized vinyl chlorides containing little or no copolymerized co-monomers. Useful co-monomers, if desired, include mono-unsaturated ethylenically unsaturated monomers copolymerizable with vinyl chloride monomers by addition polymerization. Useful co-monomers include other vinyl monomers such as vinyl acetate, ethers, and vinylidene chloride. Other useful co-monomers include mono, including acrylics such as lower alkyl acrylates or methacrylates, acrylic and methacrylic acids, lower alkenyl olefins, vinyl aromatics such as styrene and styrene derivatives, and vinyl esters and ethers. -Ethylenically unsaturated monomers. Typical useful commercial co-monomers include acrylonitrile, 2-ethylhexyl acrylate, vinylidene chloride, and isobutyl ether. Useful PVC copolymers may contain from about 0.1% to about 10% or 15% by weight, preferably from about 0.5% to about 5% by weight of copolymerized co-monomer.

Chlorinated PVC copolymers can be obtained by chlorinating the PVC copolymer using conventional methods as described in US Pat. No. 2,996,489, which is incorporated herein by reference.

Preferred PVC is suspension polymerized vinyl chloride, but less preferred mass (bulk) polymerized vinyl chloride may be useful.

The PVC of the present invention has a K-value of about 50 to about 90 when the K-value is measured by using 0.2 g of resin in cyclohexanone in 100 ml at 30 ° C. according to ASTM D 1243, preferably about 60 to about 80.

Plasticizer

The poly (vinyl halide) used in the present invention is required to be flexible. Plasticizers are added to the poly (vinyl halide) to form flexible thermoplastic polymers. Any conventional plasticizer known to those skilled in the art for poly (vinyl halides) is suitable for use in the present invention. When PVC is used, the most common plasticizers are phthalate plasticizers.

Non-limiting examples of plasticizers include phthalate plasticizers (eg, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, dibutyl phthalate or dihexyl phthalate); Straight chain dibasic acid ester plasticizers (eg, dioctyl adipate, or dioctyl sebacate); Trimellitate plasticizers; Polyester polymer plasticizers; Epoxy plasticizers (eg, epoxidized soybean oil, epoxidized linseed oil or epoxy resins); Phosphate plasticizers (eg, triphenyl phosphate, trixylyl phosphate or tricresyl phosphate). These plasticizers can be used alone or together as a mixture of two or more of them.

Commercially available plasticizers include, among other plasticizers, Palatinol 11P-E from BASF Corporation, Pallatinol TOTM from BASF Corporation, and Plas-Check 775 from Ferro Corporation. (Plas-chek 775), and Synplast NOTM from PolyOne Corporation.

Thermoplastic Uncrossed  Elastomer

Partially or fully crosslinked thermoplastic elastomers are also known as thermoplastic vulcanizates because the elastomers are partially or fully vulcanized and thus become thermoset rubbers. When the vulcanization reaction occurs, it is less flexible in processing the form of the thermoplastic vulcanizate, since the vulcanizate becomes thermoset.

Contrary to the teachings of US Patent Publication No. 20040054085, the present invention does not require any crosslinking in the elastomer. Thus, the elastomer remains completely thermoplastic, exhibits thermoplasticity, and can perform multiple thermoplastic processing steps without the complex situation associated with partial or complete crosslinking of the material.

Non-crosslinked elastomers with thermoplastics are known in the thermoplastics industry and are readily commercially available. Any olefinic elastomer capable of melt blending with poly (vinyl halide) to form an alloy is suitable for use in the present invention. Those skilled in the art will appreciate that suitable uncrosslinked elastomers such as chlorinated polyethylene (CPE) elastomers, metallocene-catalyzed ethylene-octene copolymers, or uncrosslinked ethylene propylene diene monomer terpolymers (EPDM) without undue experimentation Can be selected. In addition, without undue experimentation, those skilled in the art will appreciate that other suitable ratios from the class of additives called impact modifiers to the range of olefinic, non-crosslinking, elastomeric but processable materials such as thermoplastics Elastomers can be determined.

Commercial examples of uncrosslinked chlorinated olefin elastomers include the Duracryn 7160 NC (Advanced Polymer Alloys, Wilmington, Delaware, USA), a division of Ferro Corporation, Cleveland, Ohio. 7160 NC).

Any additive

The compounds of the present invention may comprise conventional plastic additives in an amount sufficient to obtain the required processing or performance properties of the compound. Such amounts not only waste additives but also should not be detrimental to the processing or performance of the compound. Experts in the field of compounding thermoplastics refer to articles such as the Plastics Additives Database (2004) from Plastics Design Library (www.williamandrew.com) without undue experimentation for inclusion into the compounds of the present invention. It can be chosen from many different forms of additives.

Non-limiting examples of optional additives include adhesion promoters; Biocides (antibiotics, antimicrobials, and mildewcides), anti-fogging agents; Antistatic agents; Binders, expanding agents and blowing agents; Dispersing agent; Fillers and extenders; Fire and flame retardants and smoke suppressants; Impact modifiers; Initiator; slush; Mica; Pigments, colorants and dyes; Plasticizers; Processing aids; Release agents; Silanes, titanates and zirconates; Slip agents and anti-blocking agents; Stabilizer; Stearate; Ultraviolet humectants; Viscosity modifiers; Wax; And combinations thereof.

Table 1 shows preferred components that are acceptable for the alloy of the present invention.

TABLE 1 ingredient product name Manufacturer Allowable range Desirable range Poly (vinyl halide) Oxyvinyl 220F Oxyvinyls 25-50% 30-40% Plasticizer Sinplast NOTM Poly One 20-45% 30-40% Uncrosslinked elastomer Durac Clean 7160 NC Advanced Polymer Alois 5-50% 10-30% Mixed Metal Stabilizer CPS 507 Amfine Chemicals 0.5-2.5% 1-2% Internal lubricant AX-71 Ampine Chemicals 0.01-0.2% 0.05-0.10% Fatty acid ester LS-10 Ampine Chemicals 0.01-0.2% 0.05-0.10% Phosphite stabilizer CPL-1551 Ampine Chemicals 0.2-2% 0.5-1% Pigment dispersion 642H V Dk Pewter MB Poly One Corporation 0.1-5% 0.5-2.5% Polyvinyl chloride
Resin dispersion Vinnolit P70
Binollet
0.5-5%
2-5%

Processing

The preparation of the compounds of the present invention is not complicated. The compounds of the present invention can be prepared batchwise or in a continuous operation.

Mixing in a continuous process is typically carried out in an extruder which is raised to a temperature sufficient to melt the polymer matrix, by adding solid component additives of any optional additives downstream of the extruder head. The extruder speed may range from about 50 to about 500 revolutions per minute (rpm), preferably from about 100 to about 300 rpm. Typically, the product from the extruder is pelletized into a polymer product for subsequent extrusion or molding.

In the present invention, dry blending of PVC and other non-elastomeric components is preferred before extruding the PVC and the uncrosslinked elastomer.

Mixing in the batch process is typically performed in a Banbury mixer which is raised to a temperature sufficient to melt the polymer matrix allowing the addition of any optional solid component additive. The mixing speed is from 60 to 1000 rpm and the mixing temperature can be ambient temperature. In addition, the product from the mixer is chopped to a small size for subsequent extrusion or molding into the polymer product.

Alternatively, mixing in a batch process may be performed in a Henschel mixer, which typically does not bring the polymer matrix to a melting temperature, but through mechanical action. The mixing speed ranges from 60 to 1000 rpm and the mixing temperature may be ambient temperature.

The alloys of the present invention may also be formed into powders, cubes, or pellets for further extrusion or molding into polymeric articles.

Subsequent extrusion or molding techniques are known to those skilled in the art of thermoplastic polymer engineering. Without undue experimentation ("Extrusion, The Definitive Processing Guide and Handbook"; "Handbook of Molded Part Shrinkage and Warpage"; "Specialized Molding Techniques"; "Rotational Molding Technology"; and "Handbook of Mold, Tool and Die Repair Welding) By referring to the all published by Plastics Design Library (www.williamandrew.com), one skilled in the art can use the alloys of the present invention to produce products of any reasonable shape and appearance.

After extrusion or other mixing, preferably slush molding can be used to form useful products from the alloy of the present invention. Slush moldings use an open-end mold design that forms a product as a polymer skin (eg, a vehicle dashboard). Those of ordinary skill in the art are: US Pat. No. 6,797,222 to Hausmann et al. And US Pat. No. 2,736,925; US Patent No. 3,039,146; The principle of slush molding can be understood by referring to EP 0 339 222, EP 0 476 742 and PCT Patent WO 0207946.

In summary, slush molding generally comprises the following steps: a) an open-air tank is first suitable in polymer and in a grain size of typically less than 500 micrometers; Filling with powder; b) a mold generally electroplated with nickel is then heated to a given temperature; c) the tank and the mold are then coupled by suitable coupling means into a closed system; d) moving the system so that the tank delivers the powder into the mold to obtain a partially or fully melted uniform layer of powder that adheres to the mold; e) opening the closed system after bringing it back to initial conditions; In this step, possible excess polymer powder can be deposited again in the tank and thereby regenerated; f) heating the mold to complete the melting; g) cooling the mold with suitable cooling means; h) peeling off the formed sheet as a semi-finished product which can be assembled with the support to obtain the final product in the form of an instrument panel, door panel, etc. for the interior decoration of the vehicle.

The alloy of the present invention is particularly suitable for use with slush molding processing techniques because the non-crosslinked elastomers improve the melt flow of the alloy to reduce the likelihood of pinholes and other processing defects during the formation of the polymer skin. Because.

Utility of the present invention

The alloy of the present invention is particularly suitable for producing thin polymer film products for imitation leather, imitation fabrics and other products used in residential and automotive interiors using slush molding technology. For example, a "polymer skin" can be formed by using slush moldings from the alloy of the present invention. These polymer skins have a very large length or width to thickness appearance ratio and can form random or repeating patterns of grain appearance in leather, wool or other natural items due to the shape of the mold.

Example

The formulation of the alloy of the invention as defined in Table 2 was made through slush molding by using the processing parameters shown in Table 3 to produce polymer skins having the performance characteristics shown in Table 4.

TABLE 2 ingredient product name Manufacturer weight%
Poly (vinyl halide) Oxyvinyl 220F Oxyvinyls 37.0 Plasticizer Sinplast NOTM Synergistics 35.1 Uncrosslinked elastomer Durac Clean 7160 NC Advanced Polymer Alois 20 Mixed Metal Stabilizer CPS 507 Amfine Chemicals 1.5 Internal lubricant AX-71 Ampine Chemicals 0.1 Fatty acid ester LS-10 Ampine Chemicals 0.1 Phosphite stabilizer CPL-1551 Ampine Chemicals 0.7 Pigment dispersion 642H V Dk
Fiuter MB Poly One Corporation 1.8 Polyvinyl chloride
Resin dispersion Vinollit P70 Binollet 3.7

TABLE 3 Processing condition Device Henschel mixer for dry blending PVC Extruder Mold machine speed 800 rpm, 550 rpm 350 rpm N / A Order of addition Step 1. Addition of poly (vinyl halides), mixed metal stabilizers, internal lubricants, fatty acid esters, phosphite stabilizers, pigment dispersions,
Step 2. plasticizer addition,
Step 3. Add PVC Resin Dispersion Non-crosslinked elastomer and PVC dry blend added to the neck N / A Preheating temperature N / A Zone 1: 275 ° C
Zone 2: 275 ° C
Zone 3: 300 ℃
Zone 4: 300 ℃
Zone 5: 325 ° C
Zone 6: 325 ° C
Zone 7: 325 ° C
Zone 8: 325 ° C
Zone 9: 330 ℃
Zone 10: 330 ° C N / A Final melting temperature N / A 200 ℃ 230 ℃ Residence time N / A N / A 20 seconds

Table 4 Performance characteristics exam result Elongation,
ASTM D638, 500mm / min 456%



expansibility,
ASTM D638,
500mm / min 11.9 MPa importance,
ASTM D792 1.188 Hardness, Shore A, 15 Second Delay, ASTM D1004 68 Shore A Glass transition temperature, E "base, DMA analysis -37.6 ℃ Xenon Arc Weatherometer, SAEJ1885 601.6kJ / m ^2-
DE ^* = 0.3 1240.8 kJ / m ^2-
DE ^* = 0.2 1504kJ / m ^2-
DE ^* = 0.3

The invention is not limited to the above embodiments. Claims are as follows.

Claims (18)

Slush molded products made from thermoplastic alloys comprising poly (vinyl halides), plasticizers, and thermoplastic olefin-based uncrosslinked elastomers, wherein the K-value of the poly (vinyl halides) is at 30 ° C. 50 to 90 when measured using 0.2 g poly (vinyl halide) in 100 ml cyclohexanone. The process of claim 1 wherein the poly (vinyl halide) comprises poly (vinyl chloride) or chlorinated poly (vinyl chloride), The poly (vinyl halide) is present in an amount ranging from 0.1 to 15% by weight and is selected from the group consisting of acrylonitrile, 2-ethylhexyl acrylate, vinylidene chloride, and isobutyl ether (co -monomer), Plasticizer (a) a phthalate plasticizer selected from the group consisting of di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, dibutyl phthalate and dihexyl phthalate; (b) a straight chain dibasic acid ester plasticizer selected from the group consisting of dioctyl adipate and dioctyl sebacate; (c) trimellitate plasticizers; (d) polyester polymer plasticizers; (e) an epoxy plasticizer selected from the group consisting of epoxidized soybean oil, epoxidized linseed oil and epoxy resins; (f) phosphate plasticizers selected from the group consisting of triphenyl phosphate, trixylyl phosphate and tricresyl phosphate; or (g) mixtures thereof, The elastomer remains completely thermoplastic, exhibits thermoplasticity, and can be melt blended with poly (vinyl halide) again and again to form an alloy, The elastomer is selected from the group consisting of chlorinated polyethylene elastomers, metallocene-catalyzed ethylene-octene copolymers, and uncrosslinked ethylene propylene diene monomer terpolymers, The poly (vinyl halide) is present in an amount ranging from 25 to 50% by weight of the product; The plasticizer is present in an amount ranging from 20 to 45 weight percent of the product; Uncrosslinked elastomer is present in an amount ranging from 5 to 50% by weight of the product, The product is an adhesion promoter; Biocides (antibiotics, antimicrobials, and mildewcides), anti-fogging agents; Antistatic agents; Binders, expanding agents and blowing agents; Dispersing agent; Fillers and extenders; Fire and flame retardants and smoke suppressants; Impact modifiers; Initiator; slush; Mica; Pigments, colorants and dyes; Processing aids; Release agents; Silanes, titanates and zirconates; Slip agents and anti-blocking agents; Stabilizer; Stearate; Ultraviolet absorber; Viscosity modifiers; Wax; Or a combination further thereof. a) of poly (vinyl halide), plasticizer, and olefin-based uncrosslinked elastomer having a K-value of 50 to 90 as measured using 0.2 g poly (vinyl halide) in 100 ml of cyclohexanone at 30 ° C. Filling the powder mixture into an open-air tank; b) heating the mold to a temperature of 190 ° C to 240 ° C; c) coupling the tank and the mold by a coupling means; d) moving the system to cause the tank to deliver the powder mixture onto the mold to obtain a partially or fully molten powder layer that adheres to the mold; e) opening a closed system; f) heating the mold to complete melting of the powder mixture to form a polymer skin on the mold; g) cooling the mold with cooling means; And h) removing the formed polymer skin from the mold, wherein the product of claim 1 is prepared. A polymer skin prepared by the method of claim 3. A polymer skin comprising the product of claim 1. delete delete delete delete delete delete delete delete delete delete delete delete delete